Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium Outperforms Silicon.

Authors

Kelling J. Donald, University of RichmondFollow
Supreeth Prasad
Kaitlin Wilson

DOI

10.1002/cplu.202100294

Abstract

The nature of halogen bonding under different dielectric conditions remains underexplored, especially for inorganic systems. The structural and energetic properties of model halogen bonded complexes (R₃M−I—NH₃ for R=H and F, and M=C, Si, and Ge) are examined computationally for relative permittivities between 1 and 109 using an implicit solvent model. We confirm and assess the exceptionally high maximum potentials at the sigma hole on I (V_s,max) in F₃Ge−I relative to cases where M=C or Si. In particular, Ge far outperforms Si in mediating inductive effects. Linear relationships, typically with R2 >0.97, are identified between V_s,max, the full point charge on I in R₃M−I, and the interaction energy, and optimized I—N distance in the complexes. An anomalous trend is identified in which, for each M, F₃M−I—NH₃ becomes less stable as the optimized I—N distance gets shorter in different dielectric environments; it is explained using the F−I—NH₃ complex as a reference.

Document Type

Article

Publication Date

8-4-2021

Publisher Statement

Copyright © 2021, Chemistry Europe.

DOI: https://doi.org/10.1002/cplu.202100294.

Recommended Citation

Donald, Kelling J., Supreeth Prasad, and Kaitlin Wilson. “Group 14 Central Atoms and Halogen Bonding in Different Dielectric Environments: How Germanium Outperforms Silicon.” Chempluschem Online First (August 4, 2021). https://doi.org/10.1002/cplu.202100294.